KR20190011950A - Copolymer and organic solar cell comprising the same - Google Patents

Abstract

The present invention relates to a copolymer having excellent aggregation properties and crystallinity, and an organic solar cell including the copolymer. The copolymer of the present invention comprises: a repeating unit derived from a compound represented by chemical formula 1; and a copolymer including a conjugate monomer.

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymer and an organic solar cell comprising the same. BACKGROUND ART [0002]

The present invention relates to copolymers and organic solar cells comprising them.

Organic solar cells are devices that can convert solar energy directly into electric energy by applying photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on the material constituting the thin film. A typical solar cell is made of p-n junction by doping crystalline silicon (Si), which is an inorganic semiconductor. Electrons and holes generated by absorption of light are diffused to the p-n junction, accelerated by the electric field, and moved to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuit to the solar power entering the solar cell, and is achieved up to 24% when measured under the current standardized virtual solar irradiation conditions. However, since conventional inorganic solar cells have already been limited in economic efficiency and supply / demand of materials, organic semiconductor solar cells, which are easy to process, have various functions and are inexpensive, are seen as long-term alternative energy sources.

Solar cells are important to increase efficiency so that they can output as much electrical energy as possible from solar energy. In order to increase the efficiency of such a solar cell, it is also important to generate as much excitons as possible in the semiconductor, but it is also important to draw out generated charges without loss. One of the causes of loss of charge is that the generated electrons and holes are destroyed by recombination. Various methods have been proposed as methods for transferring generated electrons and holes to electrodes without loss, but most of them require additional processing, which may increase the manufacturing cost.

Two-layer organic photovoltaic cells (C. W. Tang, Appl. Phys. Lett., 48, 183 (1986) Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science, 270, 1789. (1995)).

It is an object of the present invention to provide a copolymer and an organic solar cell including the same.

The present invention relates to a resin composition comprising a repeating unit derived from a compound represented by the following general formula (1): And

A copolymer comprising a conjugated monomer is provided.

[Chemical Formula 1]

In Formula 1,

m1, m2, q1 and q2 are the same or different and each independently represents an integer of 0 to 5,

When m1, m2, q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,

A1 and A1 'are the same or different and each independently represents a halogen group; A substituted or unsubstituted boron group; And or -SnR _a R _b R _c,

X1, X2 and Z1 to Z4 are the same or different from each other and each independently represents S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR '

R _a , R _b , R _c , R, R ', R 1 to R 6 and R 11 to R 18 are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

Another embodiment of the present specification is a compound represented by the following formula 1: And

And reacting a second compound represented by the following formula (2).

[Chemical Formula 1]

(2)

In the above Formulas 1 to 3,

m1 and m2 are the same or different from each other and each independently represents an integer of 0 to 5,

When m1 and m2 are each 2 or more, the structures in parentheses are the same or different from each other,

q1 and q2 are the same or different and each independently represents an integer of 1 to 5,

When q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,

A1, A1 ', A2 and A2' are the same or different from each other and each independently represents a halogen group; A substituted or unsubstituted boron group; And or -SnR _a R _b R _c,

E1 is a first conjugated monomer,

X1, X2 and Z1 to Z5 are the same or different from each other and each independently represents S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR '

R _a , R _b , R _c , R, R ', R ", R 1 to R 4 and R 11 to R 18 are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

Another embodiment of the present disclosure relates to a liquid crystal display comprising a first electrode;

A second electrode facing the first electrode; And

And at least one organic layer disposed between the first electrode and the second electrode and including a photoactive layer,

Wherein at least one of the organic material layers comprises the copolymer.

The copolymer according to one embodiment of the present invention exhibits planarity and is excellent in aggregation characteristics and crystallinity

The copolymer according to one embodiment of the present disclosure may have the effect of decreasing the bandgap and / or increasing the amount of absorption of light. Accordingly, when the organic solar battery is applied to the organic solar battery, a high current value (Isc) can be exhibited, thereby exhibiting excellent efficiency.

The copolymer according to one embodiment of the present invention has a high efficiency and an appropriate solubility at the same time, which is economically advantageous in time and / or cost in manufacturing the device.

The copolymer according to one embodiment of the present invention can be used alone or in combination with other materials in organic solar cells.

1 is a view illustrating an organic solar cell according to an embodiment of the present invention.
2 is an NMR spectrum of Compound 1-d.
3 is a graph showing the MS spectrum of the compound 1-d.
4 shows the MS spectrum of compound 1-f.
5 is a graph showing the MS spectrum of Compound 1-g.

Hereinafter, the present invention will be described in detail.

One embodiment of the present specification is a compound having a repeating unit derived from the compound represented by Formula 1 above; And a conjugated monomer.

The repeating unit derived from the compound represented by the formula (1) includes a thiophene having an electron donating property and a benzothiadiazole having an electro withdrawing property. Therefore, intramolecular interaction between the thiophene and the benzothiadiazole provides excellent planarity, aggreagation, and improved crystallinity.

In addition, the repeating unit derived from the compound represented by the formula (1) has excellent crystallinity because the repeating unit has a region-regular in which R1 and R2 are substituted at a certain position.

As used herein, "positional regularity" means that a substituent is provided in a certain direction in a structure in a polymer. For example, in Formula 1, R 1 and R 2 are substituted at positions relatively far from the phenyl group substituted by R 1 to R 4.

As used herein, the term " derived " means that a bond between at least two adjacent elements in the compound is broken, or a new bond is formed as hydrogen or a substituent is released, and the unit derived from the compound is a main chain and / Or a side chain. The above unit may be included in the main chain in the copolymer to form a copolymer.

As used herein, the term " repeating unit " means a structure in which a unit derived from a monomer is repeatedly contained in a copolymer, and refers to a structure in which a plurality of monomers of one kind are bonded in the copolymer by polymerization.

In one embodiment of the present specification, the "repeating unit derived from the compound represented by formula (1)" may include the following structure in the main chain.

In the above structure, R 1 to R 6, R 11 to R 18, Z 1 to Z 4, and X 1 and X 2 are the same as defined in formula (1).

In this specification, when a part is referred to as "including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

As used herein, " combination " means connecting several structures or connecting different types of structures.

Examples of substituents in the present specification are described below, but are not limited thereto.

는 다른 치환기, 단량체 또는 결합부에 결합되는 부위를 의미한다.In the present specification,

Quot; means a moiety bonded to another substituent, monomer, or binding site.

In the present specification, a monomer may mean a repeating unit contained in a polymer. For example, the conjugated monomer may refer to a repeating unit derived from a conjugated monomer contained in the polymer.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" A halogen group; A nitrile group; A nitro group; Imide; Amide group; Carbonyl group; An ester group; A hydroxy group; An alkyl group; A cycloalkyl group; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; An alkenyl group; Silyl group; Siloxyl group; Boron group; An amine group; Arylphosphine groups; Phosphine oxide groups; An aryl group; And a heterocyclic group, or that two or more of the substituents in the above-exemplified substituents are substituted with a substituent to which they are linked, or have no substituent. For example, "a substituent to which at least two substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the amide group may be substituted with nitrogen of the amide group by hydrogen, a straight chain, branched chain or cyclic alkyl group of 1 to 30 carbon atoms or an aryl group of 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with an ester group oxygen or carbon with a straight chain, branched chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a group having 3 to 30 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, It is not.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

In this specification, the amine group is -NH ₂ ; An alkylamine group; N-arylalkylamine groups; An arylamine group; An N-arylheteroarylamine group; An N-alkylheteroarylamine group, and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine, dimethylamine, ethylamine, diethylamine, phenylamine, naphthylamine, biphenylamine, anthracenylamine, 9-methyl- , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group and triphenylamine group, but are not limited thereto.

In the present specification, the N-alkylarylamine group means an amine group in which N of the amine group is substituted with an alkyl group and an aryl group.

In the present specification, the N-arylheteroarylamine group means an amine group in which N in the amine group is substituted with an aryl group and a heteroaryl group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which N in the amine group is substituted with an alkyl group and a heteroarylamine group.

In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthio group, the alkylsulfoxy group and the N-alkylheteroarylamine group is the same as the alkyl group described above. Specific examples of the alkyloxy group include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group and an octylthio group. Examples of the alkylsulfoxy group include a mesyl group, an ethylsulfoxy group, a propylsulfoxy group, And the like, but the present invention is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, However, the present invention is not limited thereto.

In this specification, the boron group is -BR R ₁₀₀ may be ₂₀₀ days, wherein R ₁₀₀ and R ₂₀₀ are the same or different and each is independently hydrogen; heavy hydrogen; halogen; A nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted, straight or branched chain alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

In the present specification, the phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably 10 to 30 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the N-arylalkylamine group, the N-arylheteroarylamine group and the arylphosphine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, a m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6- trimethylphenoxy group, a p- Naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group and 9-phenanthryloxy group and the arylthioxy group includes phenylthio group, 2- Methylphenylthio group, 4-tert-butylphenylthio group and the like, and examples of the arylsulfoxy group include a benzene sulfoxide group and a p-toluenesulfoxy group. However, the present invention is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heterocyclic group includes at least one non-carbon atom or hetero atom, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, , An isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, But are not limited to, phenanthroline, thiazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, phenothiazyl and dibenzofuranyl groups.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group having two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the above-mentioned heterocyclic group.

In one embodiment of the present invention, the conjugated monomer may be one kind of conjugated monomer.

In one embodiment of the present invention, the conjugated monomer may be two kinds of conjugated monomers. That is, in one embodiment of the present disclosure, the conjugated monomer may comprise a first conjugated monomer and a second conjugated monomer different from the first conjugated monomer.

As used herein, a "conjugated monomer" means that two or more multiple bonds in the structure of a compound are present between one single bond and exhibit an interaction. Here, the conjugated monomer means both the first conjugated monomer and the second conjugated monomer.

In the present specification, the conjugated monomer may mean a repeating unit derived from a conjugated monomer contained in a polymer.

In one embodiment of the present invention, the conjugated monomer may be a combination of one or more groups selected from the group consisting of a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group and a substituted or unsubstituted divalent heterocyclic group have.

In the present specification, the description of the aforementioned alkenyl group can be applied except that the alkenylene group is divalent.

In the present specification, the description of the aryl group described above can be applied, except that the arylene group is divalent.

In the present specification, the description of the aforementioned heterocyclic group can be applied, except that the divalent heterocyclic group is a divalent group.

According to one embodiment of the present disclosure, the conjugated monomer includes an electron donor structure or an electron acceptor structure.

In one embodiment of the present specification, the conjugated monomers each independently include any one of the following structures or a combination of two or more thereof.

In the above structure,

a, a ', b and b' are each an integer of 1 to 5,

When a, a ', b and b' are each 2 or more, the substituents in the parentheses are the same or different from each other,

X11 to X30 and X33 to X40 are the same as or different from each other, and are each independently S, O, Se, Te, NR _d, CR _d R _e, SiR _d R _e, or PR _d GeR _d R _e,

X31 and X32 are the same or different, and are each independently C, Si or Ge,

R101 through R124, R _d and R _e are the same or different and are each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present disclosure, the conjugated monomer is any one of the following structures.

In the above structure,

To X11 to X14, X19, X20, X33 X40, X11 ', and X11''are the same or different and each is independently S, O, Se, Te, NR _d, CR _d R _e, SiR _d R _e, PR _d or GeR _d R _e ,

R101 to R110, R117 to R124, R101 ', R101'' , R102', R102 '', R d and R _e are the same or different and are each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present disclosure, and wherein X11 to X14, X19, X20, X33 to X40, X11 ', and X11''are the same or different and each independently S or CR _d R _e, R _d, and R _e is the same as described above.

In one embodiment of the present invention, each of X11 to X14, X19, X20, X33 to X36, X39, X40, X11 'and X11 "is S each.

In one embodiment of the present disclosure, X37 and X38 are CR _d R _e , _and R _d and R _e substituted or unsubstituted aryl group.

In one embodiment of the present invention, R101 to R110, R117 to R124, R101 ', R101', R102 'and R102' 'are the same or different and each independently hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present disclosure, R101, R101 ', R101 ", R102, R102' and R102" are the same or different and each independently hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkoxy group.

In one embodiment of the present disclosure, R101, R101 ', R101 ", R102, R102' and R102" are the same or different and each independently hydrogen; An alkyl group having 1 to 15 carbon atoms; Or a substituted or unsubstituted alkoxy group having 1 to 15 carbon atoms.

In one embodiment of the present invention, R103 and R108 are the same or different and each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R104 and R107 are hydrogen.

In one embodiment of the present specification, R105 and R106 are the same or different and each independently represents a substituted or unsubstituted alkoxy group.

In one embodiment of the present invention, R105 and R106 are the same or different and each independently a substituted or unsubstituted alkoxy group having 1 to 15 carbon atoms.

In one embodiment of the present specification, R109 and R110 are the same or different and are each independently a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R109 and R110 are the same or different and each is a heterocyclic group independently substituted with an alkyl group.

In one embodiment of the present specification, R109 and R110 are the same or different and each independently a thiophen group substituted with an alkyl group.

In one embodiment of the present specification, R121 and R122 are the same or different and are each independently a halogen group.

In one embodiment of the present specification, R121 and R122 are fluorine.

In one embodiment of the present specification, R117 and R120 are the same or different and each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R117 and R120 are the same or different and each independently a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms.

In one embodiment of the present invention, R117 and R120 are the same or different and each independently a branched alkyl group having 1 to 15 carbon atoms.

In one embodiment of the present specification, R118 and R119 are hydrogen.

In one embodiment of the present specification, R123 and R124 are hydrogen.

In one embodiment of the present invention, the copolymer includes a unit represented by the following general formula (1-1) or (1-2).

[Formula 1-1]

[Formula 1-2]

In the above formulas 1-1 and 1-2,

m1, m2, m1 ', m2', q1, q2, q1 'and q2' are the same or different and each independently an integer of 0 to 5,

When m1, m2, m1 ', m2', q1, q2, q1 'or q2' are each 2 or more, the structures in parentheses are the same or different,

X1, X2, X1 ', X2', Z1 to Z4 and Z1 'to Z4' are the same or different from each other and are independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ' ,

E1 is a first conjugated monomer,

E2 is a second conjugated monomer,

R, R ', R1 to R6, R1' to R6 ', R11 to R18 and R11' to R18 'are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

f is a mole fraction, 0 < l < 1,

g is a molar fraction, 0 < m < 1,

f + g = 1,

n is the number of repeating units of the unit, and is an integer of 1 to 10,000.

In one embodiment of the present specification, R1 to R6 and R11 to R18 are the same or different from each other, and each independently hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

Wherein R1 to R6 and R11 to R18 are the same or different from each other, and each independently hydrogen; A halogen group; Or a substituted or unsubstituted alkoxy group.

In one embodiment of the present invention, R 1 and R 2 are the same or different and are each independently a halogen group.

In one embodiment of the present specification, R 1 and R 2 are fluorine.

In one embodiment of the present invention, R 3 and R 5 are the same or different and each independently represents a substituted or unsubstituted alkoxy group.

In one embodiment of the present invention, R 3 and R 5 are the same or different and each independently a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.

In one embodiment of the present invention, R 3 and R 5 are the same or different and each independently a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.

In one embodiment of the present invention, R 3 and R 5 are the same or different and each independently an alkoxy group having 1 to 15 carbon atoms.

In one embodiment of the present disclosure, R4 and R6 are hydrogen.

In one embodiment of the present invention, R11 to R18 are hydrogen.

In one embodiment of the present disclosure, X1, X2 and Z1 to Z4 are S.

In one embodiment of the present specification, R1 'to R6' and R11 'to R18' are the same or different from each other, and each independently hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present invention, R1 'and R2' are the same or different from each other, and each independently represents a halogen group.

In one embodiment of the present specification, R1 'and R2' are fluorine.

In one embodiment of the present invention, R3 'and R5' are the same or different and each independently represents a substituted or unsubstituted alkoxy group.

In one embodiment of the present invention, R3 'and R5' are the same or different and each independently a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.

In one embodiment of the present invention, R 3 'and R 5' are the same or different from each other, and each independently represents a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.

In one embodiment of the present invention, R3 'and R5' are the same or different from each other and each independently an alkoxy group having 1 to 15 carbon atoms.

In one embodiment of the present disclosure, R4 'and R6' are hydrogen.

In one embodiment of the present invention, R11 'to R18' are hydrogen.

In one embodiment of the present disclosure, X1 ', X2' and Z1 'to Z4' are S.

In one embodiment of the present invention, each of A1 and A1 'is a halogen group.

In one embodiment of the present disclosure, A1 and A1 'are bromine.

In one embodiment of the present invention, each of the conjugated monomer, the first conjugated monomer and the second conjugated monomer is any one of the following structures.

In one embodiment of the present invention, the copolymer includes units represented by the following formulas (1-3) or (1-4).

[Formula 1-3]

[Formula 1-4]

In Formulas 1-3 and 1-4,

m1, m2, m1 'and m2' are the same or different and each independently an integer of 0 to 5,

When m1, m2, m1 'and m2' are each 2 or more, the structures in parentheses are the same or different,

q1, q2, q1 'and q2' are the same or different and each independently an integer of 1 to 5,

When q1, q2, q1 'and q2' are respectively 2 or more, the structures in parentheses are the same or different from each other,

X1, X2, X1 ', X2', Z1 to Z4 and Z1 'to Z4' are the same or different from each other and are independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ' ,

E1 is a first conjugated monomer,

E2 is a second conjugated monomer,

R, R ', R1, R2, R1', R2 ', R11 to R18 and R11' to R18 'are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R51, R51 ', R52 and R52' are the same or different and each independently hydrogen; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

f is a mole fraction, 0 < l < 1,

g is a molar fraction, 0 < m < 1,

f + g = 1,

n is the number of repeating units of the unit, and is an integer of 1 to 10,000.

In one embodiment of the present invention, R 1, R 2, R 11 to R 18, X 1, X 2, Z 1 to Z 4, E 1 and E 2 in formulas 1-3 and 1-4 are the same as described above.

In one embodiment of the present invention, R51, R52, R51 'and R52' are the same or different and each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present invention, R51, R52, R51 'and R52' are the same or different and each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present invention, R51, R52, R51 'and R52' are the same or different and each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present invention, R51, R52, R51 'and R52' are the same or different and each independently a branched alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present invention, f and g are equal to or different from each other, and are respectively a real number of 0.3 to 0.7, and f + g = 1.

In one embodiment of the present disclosure, f is 0.3 and g is 0.7.

In one embodiment of the present disclosure, f is 0.7 and g is 0.3.

In one embodiment of the present disclosure, f and g are 0.5.

In one embodiment of the present disclosure, m1, m2, m1 'and m2' are 1.

In one embodiment of the present disclosure, q1, q2, q1 'and q2' are one.

In one embodiment of the present specification, the copolymer has any of the following structures.

In the above structure,

n is the number of repeating units of the unit, and is an integer of 1 to 10,000.

In one embodiment of the present invention, the terminal group of the copolymer is a substituted or unsubstituted aryl group.

In one embodiment of the present invention, the terminal group of the copolymer is an aryl group substituted with a halogen group.

In one embodiment of the present invention, the terminal group of the copolymer is a benzotrifluryl group.

In one embodiment of the present disclosure, the number average molecular weight of the copolymer is from 2,000 g / mol to 30,000,000 g / mol. Preferably, the number average molecular weight of the copolymer is from 5,000 g / mol to 10,000,000 g / mol. More preferably, the number average molecular weight of the copolymer is from 10,000 g / mol to 5,000,000 g / mol.

In one embodiment of the present disclosure, the copolymer may have a molecular weight distribution (PDI) of from 1 to 100. Preferably, the copolymer has a molecular weight distribution of from 1 to 3.

One embodiment of the present disclosure is directed to a compound of formula 1, And

And reacting a second compound represented by the following formula (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

m1 and m2 are the same or different from each other and each independently represents an integer of 0 to 5,

When m1 and m2 are each 2 or more, the structures in parentheses are the same or different from each other,

q1 and q2 are the same or different and each independently represents an integer of 1 to 5,

When q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,

A1, A1 ', A2 and A2' are the same or different from each other and each independently represents a halogen group; A substituted or unsubstituted boron group; And or -SnR _a R _b R _c,

E1 is a first conjugated monomer,

X1, X2 and Z1 to Z5 are the same or different from each other and each independently represents S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR '

R _a , R _b , R _c , R, R ', R ", R 1 to R 4 and R 11 to R 18 are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present invention, the first compound represented by Formula 1; And reacting the second compound represented by Formula 2 with a first compound; A second compound; And a third compound represented by the following general formula (3).

(3)

In Formula 3,

A3 and A3 'are the same or different and each independently represents a halogen group; A substituted or unsubstituted boron group; And or -SnR _a R _b R _c,

R _a , R _b And R &lt; _c &gt; are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

E2 is a second conjugated monomer different from the first conjugated monomer.

That is, in one embodiment of the present specification, the method for producing the copolymer may include reacting two kinds of compounds, or may include reacting three kinds of compounds. Wherein the two compounds are the first compound represented by Formula 1; And the second compound represented by Formula 2, wherein the three compounds are the first compound; A second compound; And the third compound represented by the formula (3).

In one embodiment of the present specification, A2, A2 ', A3 and A3' are the same or different from each other and each independently represents a halogen group or -SnR _a R _b R _c , and R _a , R _b and R _c As described above.

In one embodiment of the present disclosure, the A2, A2 ', A3 and A3' is the same or different and each is independently a bromine or _{-SnR a R b R c, R} a, R b and R _c is a methyl group to be.

In one embodiment of the present invention, E1 in Formula 2 and E2 in Formula 3 are the same as defined in the copolymer. For example, E1 and E2 are different from each other and each represent any one of the following structures.

In one embodiment of the present disclosure, the solvent may be chlorobenzene, dichlorobenzene, and trichlorobenzene.

In one embodiment of the present invention, the content of the second compound in the solution is 0.3 mol to 0.7 mol based on 1 mol of the first compound.

In one embodiment of the present disclosure, the content of the third compound in the solution is 0.3 mol to 0.7 mol based on 1 mol of the first compound.

In one embodiment of the present specification, the solution means that the first compound and the second compound are dissolved in the solvent.

In one embodiment of the present invention, the method for producing the copolymer includes a step of dissolving the first compound, the second compound and the third compound in the solvent, followed by reflux at 90 ° C to 150 ° C.

An embodiment of the present disclosure includes a first electrode;

A second electrode facing the first electrode; And

And at least one organic layer disposed between the first electrode and the second electrode and including a photoactive layer,

Wherein at least one of the organic material layers comprises the copolymer.

1 shows an organic solar cell according to an embodiment of the present invention including a substrate 101, a first electrode 102, a hole transport layer 103, a photoactive layer 104 and a second electrode 105 to be.

In one embodiment of the present disclosure, the organic solar cell may further include an additional organic layer. The organic solar cell can reduce the number of organic layers by using organic materials having various functions at the same time.

In one embodiment of the present disclosure, the organic solar cell includes a first electrode, a photoactive layer, and a second electrode. The organic solar cell may further include a substrate, a hole transporting layer, and / or an electron transporting layer.

In one embodiment of the present disclosure, the photoactive layer comprises the copolymer.

In one embodiment of the present invention, the organic material layer includes a hole transport layer, a hole injection layer, or a layer that simultaneously transports holes and holes, and the hole transport layer, the hole injection layer, And the copolymer.

In another embodiment, the organic material layer may include an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport, and the electron injection layer, the electron transport layer, And the copolymer.

In one embodiment of the present disclosure, the first electrode is an anode and the second electrode is a cathode. In another embodiment of the present disclosure, the first electrode is a cathode and the second electrode is an anode.

In one embodiment of the present disclosure, the organic solar cell may be arranged in the order of the cathode, the photoactive layer, and the anode, and may be arranged in the order of the anode, the photoactive layer, and the cathode, but is not limited thereto.

In another embodiment, the organic solar cell may be arranged in the order of an anode, a hole transporting layer, a photoactive layer, an electron transporting layer and a cathode, and may be arranged in the order of a cathode, an electron transporting layer, a photoactive layer, a hole transporting layer, , But is not limited thereto.

In one embodiment of the present disclosure, the photoactive layer comprises an electron donor and a receiver, wherein the electron donor comprises the copolymer.

In one embodiment of the present disclosure, the electron acceptor material may be selected from the group consisting of fullerene, fullerene derivatives, vicoprofoins, semiconducting elements, semiconducting compounds, and combinations thereof. Specifically, the electron acceptor material may be a PC ₆₀ BM (phenyl C ₆₀ -butyric acid methyl ester), a PC ₆₁ BM (phenyl C ₆₁ -butyric acid methyl ester), or a PC ₇₁ BM (a phenyl C ₇₁ -butyric acid methyl ester) .

In one embodiment of the present disclosure, the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ). The electron donor material and the electron acceptor material may be mixed in a ratio (w / w) of 1:10 to 10: 1. Specifically, the electron donor material and the electron acceptor material may be mixed in a ratio of 1: 1 to 1:10 (w / w), and more specifically, the electron donor material and the electron acceptor material may be mixed in a ratio of 1: (W / w). Optionally, the electron donor material and the electron acceptor material may be mixed in a ratio (w / w) of 1: 1 to 1: 3.

In one embodiment of the present invention, the photoactive layer is a bilayer structure including an n-type organic layer and a p-type organic layer, and the p-type organic layer includes the copolymer.

In this specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and is not limited as long as it is a substrate commonly used in organic solar cells. Specific examples include glass or polyethylene terephthalate, polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

The anode electrode may be a transparent material having excellent conductivity, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The method of forming the anode electrode is not particularly limited and may be applied to one surface of the substrate or may be coated in a film form using, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing . &Lt; / RTI &gt;

When the anode electrode is formed on a substrate, it may undergo cleaning, moisture removal and hydrophilic reforming processes.

For example, the patterned ITO substrate is sequentially cleaned with a detergent, acetone, and isopropyl alcohol (IPA), and then heated on a heating plate at 100 ° C to 150 ° C for 1 minute to 30 minutes, preferably at 120 ° C for 10 minutes Dried, and the substrate surface is hydrophilically reformed when the substrate is completely cleaned.

Through such surface modification, the junction surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. Further, in the modification, the formation of the polymer thin film on the anode electrode is facilitated, and the quality of the thin film may be improved.

The pretreatment techniques for the anode electrode include a) surface oxidation using a parallel plate discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet radiation in vacuum, and c) oxygen generated by the plasma And a method of oxidizing using a radical.

One of the above methods can be selected depending on the state of the anode electrode or the substrate. However, whichever method is used, it is preferable to prevent oxygen from escaping from the surface of the anode electrode or the substrate and to suppress the residual of moisture and organic matter as much as possible. At this time, the substantial effect of the preprocessing can be maximized.

As a specific example, a method of oxidizing the surface through ozone generated using UV can be used. At this time, the ITO substrate patterned after the ultrasonic cleaning is baked on a hot plate, dried well, then put into a chamber, and is irradiated with ozone generated by reaction of oxygen gas with UV light by operating a UV lamp The patterned ITO substrate can be cleaned.

However, the method of modifying the surface of the patterned ITO substrate in the present specification is not particularly limited, and any method may be used as long as it is a method of oxidizing the substrate.

The cathode electrode may be a metal having a small work function, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure such as LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ and Al: BaF ₂ : Ba.

The cathode may be deposited in a thermal evaporator having a degree of vacuum of 5 x 10 ^{&lt; -7} &gt; torr or less, but the method is not limited thereto.

The hole transporting layer and / or the electron transporting layer material efficiently transfer electrons and holes separated from the photoactive layer to the electrode, and the material is not particularly limited.

The hole transport layer material may include poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid) (PEDOT: PSS), molybdenum oxide (MoO _x ); Vanadium oxide (V ₂ O ₅ ); Nickel oxide (NiO); And tungsten oxide (WO _x ), but the present invention is not limited thereto.

The electron transport layer material may be electron-extracting metal oxides, specifically a metal complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO _x ); Zinc oxide (ZnO); And cesium carbonate (Cs ₂ CO ₃ ), but the present invention is not limited thereto.

The photoactive layer can be formed by dissolving a photoactive material such as an electron donor and / or an electron acceptor in an organic solvent, and then applying the solution by spin coating, dip coating, screen printing, spray coating, doctor blade, brush painting, But is not limited to the method.

The process for producing the copolymer and the production of the organic solar cell including the same will be described in detail in the following Production Examples and Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Production Example 1. Preparation of Compound A

(1) Preparation of compound 1-b

To a solution of compound 1-a (10 g, 32.1 mmol), 2- (trimethylstannyl) thiophene (8.15 g, 33.0 mmol) and tetrakis (triphenylphosphine) in 150 mL toluene, Palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.74 g, 0.64 mmol) was added thereto and reacted at 110 ° C for 24 hours. After the reaction, the reaction mixture was extracted with dichloromethane, the residue was removed with magnesium sulfate (MgSO ₄ ), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: hexane) to obtain 9.51 g of compound 1-b. (Yield: 94%)

(2) Preparation of compound 1-d

(9 g, 28.56 mmol), 2-trimethylstannyl-5-trimethylsilane-thiophene (9.41 g, 29.5 mmol) and tetra (2-trimethylsilane) were added to 120 mL toluene, tetrakis (triphenylphosphine) palladium (0) was added the catalyst _{(Pd (PPh 3) 4)} (0.65g, 0.56mmol), it was reacted at 110 ℃ for 24 hours. After the reaction, the reaction mixture was extracted with dichloromethane, the residue was removed with magnesium sulfate (MgSO ₄ ), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: hexane) to obtain 10.0 g of compound 1-c. (Yield: 90%).

Compound 1-c (9.76 g, 25.00 mmol) was dissolved in 200 mL of tetrahydrofuran (THF), and 2M lithium diisopropylamide (LDA) (15.0 mL, 30.00 mmol) Lt; / RTI &gt; Trimethyltinchloride (Me ₃ SnCl) (33 mL, 33 mmol) was added thereto at the same temperature, gradually raised to room temperature, and reacted at room temperature for 3 hours. After the reaction, the mixture was extracted with dichloromethane, and the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed under reduced pressure, and the residue was recrystallized from dichloromethane and methanol to obtain 12.2 g of compound 1-d. (Yield: 88%)

2 is an NMR spectrum of Compound 1-d.

3 is a graph showing the MS spectrum of the compound 1-d.

(3) Preparation of compound 1-f

Compound 1-e (4.0 g, 5.58 mmol) and compound 1-d (7.19 g, 13 mmol) were dissolved in 60 mL of toluene and 20 mL of dimethylformamide (DMF), and tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.25 g, 0.22 mmol) was charged and gradually heated at 90 ° C., 100 ° C. and 110 ° C. for 48 hours. The residue formed upon cooling was precipitated in methanol, filtered and washed with water. Then, the solvent was evaporated through a drying process, and the residual product was purified through flash chromatography using methylene chloride and chloroform, followed by recrystallization using methylene chloride and methanol To obtain a blue solid. The solid was then washed with methanol and dried under vacuum for 24 hours to give 5 g of compound 1-f. (Yield: 67%).

4 shows the MS spectrum of compound 1-f.

(4) Preparation of compound 1-g

Compound 1-f (5.01 g, 3.75 mmol) was dissolved in 300 mL of tetrahydrofuran (THF) at room temperature under a nitrogen atmosphere and a tetrahydrofuran solution (1.0 M, 11 mL, 11 mmol, containing 5% H ₂ O) was added dropwise and the resulting product was refluxed for 2 hours. Then, 50 mL of ether and 10 mL of an aqueous solution of sodium hydrogencarbonate (NaHCO ₃ ) were added and stirred for 10 minutes. It was then washed with aqueous sodium chloride (NaCl) solution and the solvent was evaporated under vacuum conditions. The residual product was purified by flash chromatography using chloroform and then recrystallized with chloroform to obtain a dark purple solid. The solid was washed with water, methanol, hexane, ethyl acetate and acetone, and dried under vacuum for 24 hours to obtain 4.1 g of 1-g of the compound. (Yield: 92%)

5 is a graph showing the MS spectrum of Compound 1-g.

(5) Preparation of Compound A

Compound 1-g (3.75 g, 3.00 mmol) and N-bromosuccinimide (NBS) (1.17 g, 6.60 mmol) were added to 300 mL of chloroform at 0 ° C and the mixture was stirred at room temperature for 24 hours. The solvent was then evaporated and purified via flash chromatography (eluent: hexane to hexane: methylene chloride) using the residue to give 3.2 g of Compound A. (Yield: 79%) (MALDI-TOF: 1348.3 g / mol)

Production Example 2-1. Preparation of Copolymer 1

10 mL of chlorobenzene (CB), compound A (0.4 mmol) and compound B (0.4 mmol) were placed in a 100 mL flask under a nitrogen (N ₂ ) atmosphere and bubbled with nitrogen for 30 minutes. Then, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (2 mol%) was added and stirred at 110 ° C for 72 hours. 0.5 mL of Br-Benzotrifluoride was added, followed by stirring for 24 hours and cooling to room temperature. The product was then poured into chloroform, passed through a short column with silica, and poured into a mixed solution (180 mL methanol + 20 mL HCl (2 M concentration)) to filter out the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The chloroform-extracted extract was put into methanol to form a precipitate. The resulting precipitates were collected and purified, and dried under vacuum conditions to obtain 0.53 g of Copolymer 1. At this time, the number average molecular weight was measured to confirm that Copolymer 1 was produced. (Yield: 64%, number average molecular weight: 28,500 g / mol, PDI: 1.28)

Production Example 2-2. Preparation of Copolymer 2

0.38 g of Copolymer 2 was prepared in the same manner as in Production Example 2-1, except that Compound C was used instead of Compound B. (Yield: 59%, number average molecular weight: 32,100 g / mol, PDI: 1.33)

Production Example 2-3. Preparation of Copolymer 3

In the same manner as in Production Example 2-1 except that Compound D was used instead of Compound B, 0.43 g of Copolymer 3 was prepared. (Yield: 65%, number average molecular weight: 27,800 g / mol, PDI: 1.25)

Production Example 2-4. Preparation of Copolymer 4

In the same manner as in Production Example 2-1 except that Compound E was used instead of Compound B, 0.47 g of Copolymer 4 was prepared. (Yield: 66%, number average molecular weight: 41,800 g / mol, PDI: 1.67)

Production Example 2-5. Preparation of Copolymer 5

In the same manner as in Production Example 2-1 except that Compound F was used instead of Compound B, 0.33 g of Copolymer 5 was prepared. (Yield: 50%, number average molecular weight: 17,200 g / mol, PDI: 1.31)

Production Example 2-6. Preparation of Copolymer 6

In the same manner as in Production Example 2-1 except that Compound G was used instead of Compound B, 0.51 g of Copolymer 6 was prepared. (Yield: 72%, number average molecular weight: 24,800 g / mol, PDI: 1.47)

Production Example 2-7. Preparation of Copolymer 7

In the same manner as in Production Example 2-1 except that Compound H was used instead of Compound B, 0.71 g of Copolymer 7 was prepared. (Yield: 80%, number average molecular weight: 32,700 g / mol, PDI: 1.55)

Production Example 2-8. Preparation of Copolymer 8

In the same manner as in Production Example 2-1 except that Compound I was used instead of Compound B, 0.37 g of Copolymer 8 was prepared. (Yield: 55%, number average molecular weight: 13,100 g / mol, PDI: 1.36)

Production Example 2-9. Preparation of Copolymer 9

10 mL of chlorobenzene (CB), compound A (0.4 mmol), compound D (0.2 mmol) and compound J (0.2 mmol) were placed in a 100 mL flask under a nitrogen (N ₂ ) atmosphere and bubbled with nitrogen for 30 minutes. Then, a tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.11, 0.01 mmol) was added and stirred at 110 ° C for 72 hours. 0.5 mL of Br-Benzotrifluoride was added, followed by stirring for 24 hours and cooling to room temperature. The product was then poured into chloroform, passed through a short column with silica, and poured into a mixed solution (180 mL methanol + 20 mL HCl (2 M concentration)) to filter out the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The chloroform-extracted extract was put into methanol to form a precipitate. The resulting precipitates were collected and purified, and dried under vacuum conditions to obtain 0.33 g of Copolymer 9. (Yield: 65%, number average molecular weight: 21,200 g / mol, PDI: 1.48)

Example 1.

Copolymer 1 prepared in Preparation Example 2-1 was used as a donor and dissolved in chlorobenzene (CB) at a ratio of 1: 2 using PCBM as an acceptor to prepare a composite solution. At this time, the concentration was adjusted to 2.0 wt%, and the organic solar cell had the structure of ITO / ZnO / photoactive layer / MoO ₃ / Ag. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was subjected to ozone treatment for 10 minutes, followed by spin coating of the ZnO precursor solution and heat treatment at 120 ° C for 10 minutes. Then, the complex solution was filtered with a 0.45 μm PP syringe filter and then spin-coated to form a photoactive layer. Then, MoO ₃ was deposited on the photoactive layer to a thickness of 5 nm to 20 nm at a rate of 0.4 Å / s in a thermal evaporator to prepare a hole transport layer. Thereafter, Ag was deposited inside the thermal evaporator at a rate of 1 Å / s at 10 nm on the hole transport layer to produce an organic solar cell.

Example 2.

An organic solar cell was prepared in the same manner as in Example 1, except that Copolymer 3 was used instead of Copolymer 1 in Example 1.

Example 3.

An organic solar cell was prepared in the same manner as in Example 1, except that Copolymer 4 was used instead of Copolymer 1 in Example 1.

Example 4.

An organic solar cell was prepared in the same manner as in Example 1, except that Copolymer 5 was used instead of Copolymer 1 in Example 1.

Example 5.

An organic solar cell was prepared in the same manner as in Example 1, except that Copolymer 6 was used instead of Copolymer 1 in Example 1.

Example 6.

An organic solar cell was prepared in the same manner as in Example 1, except that Copolymer 7 was used instead of Copolymer 1 in Example 1.

The photoelectric conversion characteristics of the organic solar cell prepared in Examples 1 to 6 were measured under the condition of 100 mW / cm ² (AM 1.5), and the results are shown in Table 1 below.

V _oc
(V) J _sc
(mA / cm ² ) FF η
(%) Example 1 0.67 12.37 0.63 5.22 Example 2 0.68 11.80 0.61 4.89 Example 3 0.71 13.28 0.70 6.60 Example 4 0.68 10.28 0.53 3.70 Example 5 0.70 9.56 0.62 4.15 Example 6 0.81 13.27 0.63 6.77

In Table 1, V _oc is the open-circuit voltage, J _sc is the short-circuit current, FF is the fill factor, and η is the energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively. The higher the two values, the higher the efficiency of the solar cell. The fill factor is the width of the rectangle that can be drawn inside the curve divided by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency can be obtained by dividing these three values by the intensity of the irradiated light, and a higher value is preferable.

101: substrate
102: first electrode
103: Hole transport layer
104: photoactive layer
105: second electrode

Claims (17)

A repeating unit derived from a compound represented by the following formula (1); And
Copolymers comprising conjugated monomers:
[Chemical Formula 1]

In Formula 1,
m1, m2, q1 and q2 are the same or different and each independently represents an integer of 0 to 5,
When m1, m2, q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,
A1 and A1 'are the same or different and each independently represents a halogen group; A substituted or unsubstituted boron group; And or -SnR _a R _b R _c,
X1, X2 and Z1 to Z4 are the same or different from each other and each independently represents S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR '
R _a , R _b , R _c , R, R ', R 1 to R 6 and R 11 to R 18 are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group. The method according to claim 1,
Wherein the conjugated monomer comprises a first conjugated monomer and a second conjugated monomer different from the first conjugated monomer. The method according to claim 1,
Wherein the conjugated monomers each independently comprise a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a combination of one or two or more groups of a substituted or unsubstituted divalent heterocyclic group. The method according to claim 1,
Wherein the conjugated monomers each independently comprise any one or combination of two or more of the following structures:

In the above structure,
a, a ', b and b' are each an integer of 1 to 5,
When a, a ', b and b' are each 2 or more, the substituents in the parentheses are the same or different from each other,
X11 to X30 and X33 to X40 are the same as or different from each other, and are each independently S, O, Se, Te, NR _d, CR _d R _e, SiR _d R _e, or PR _d GeR _d R _e,
X31 and X32 are the same or different, and are each independently C, Si or Ge,
R101 through R124, R _d and R _e are the same or different and are each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group. The method according to claim 1,
Wherein the copolymer comprises a unit represented by the following general formula (1-1) or (1-2):
[Formula 1-1]

[Formula 1-2]

In the above formulas 1-1 and 1-2,
m1, m2, m1 ', m2', q1, q2, q1 'and q2' are the same or different and each independently an integer of 0 to 5,
When m1, m2, m1 ', m2', q1, q2, q1 'or q2' are each 2 or more, the structures in parentheses are the same or different,
X1, X2, X1 ', X2', Z1 to Z4 and Z1 'to Z4' are the same or different from each other and are independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ' ,
E1 is a first conjugated monomer,
E2 is a second conjugated monomer,
R, R ', R1 to R6, R1' to R6 ', R11 to R18 and R11' to R18 'are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
f is a mole fraction, 0 < l < 1,
g is a molar fraction, 0 < m < 1,
f + g = 1,
n is the number of repeating units of the unit, and is an integer of 1 to 10,000. The method according to claim 1,
Wherein R1 to R6 and R11 to R18 are the same or different from each other, and each independently hydrogen; A halogen group; Or a substituted or unsubstituted alkoxy group. The method according to claim 1,
Wherein X1, X2 and Z1 to Z4 are each S, The method according to claim 1,
Wherein the copolymer comprises a unit represented by the following general formula 1-3 or 1-4:
[Formula 1-3]

[Formula 1-4]

In Formulas 1-3 and 1-4,
m1, m2, m1 'and m2' are the same or different and each independently an integer of 0 to 5,
When m1, m2, m1 'and m2' are each 2 or more, the structures in parentheses are the same or different,
q1, q2, q1 'and q2' are the same or different and each independently an integer of 1 to 5,
When q1, q2, q1 'and q2' are respectively 2 or more, the structures in parentheses are the same or different from each other,
X1, X2, X1 ', X2', Z1 to Z4 and Z1 'to Z4' are the same or different from each other and are independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ' ,
E1 is a first conjugated monomer,
E2 is a second conjugated monomer,
R, R ', R1, R2, R1', R2 ', R11 to R18 and R11' to R18 'are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R51, R51 ', R52 and R52' are the same or different and each independently hydrogen; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
f is a mole fraction, 0 < l < 1,
g is a molar fraction, 0 < m < 1,
f + g = 1,
n is the number of repeating units of the unit, and is an integer of 1 to 10,000. The copolymer of claim 1, wherein the copolymer is any one of the following structures:

In the above structure,
n is the number of repeating units of the unit, and is an integer of 1 to 10,000. A first compound represented by Formula 1 below; And
Reacting a second compound represented by the following formula (2): &lt; EMI ID =
[Chemical Formula 1]

(2)

In the above formulas (1) and (2)
m1 and m2 are the same or different from each other and each independently represents an integer of 0 to 5,
When m1 and m2 are each 2 or more, the structures in parentheses are the same or different from each other,
q1 and q2 are the same or different and each independently represents an integer of 1 to 5,
When q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,
A1, A1 ', A2 and A2' are the same or different from each other and each independently represents a halogen group; A substituted or unsubstituted boron group; And or -SnR _a R _b R _c,
E1 is a first conjugated monomer,
X1, X2 and Z1 to Z5 are the same or different from each other and each independently represents S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR '
R _a , R _b , R _c , R, R ', R ", R 1 to R 4 and R 11 to R 18 are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group. The method of claim 10,
A first compound represented by Formula 1; And
The step of reacting the second compound represented by the general formula (2) comprises reacting a first compound; A second compound; And a third compound represented by the following formula (3): &lt; EMI ID =
(3)

In Formula 3,
A3 and A3 'are the same or different and each independently represents a halogen group; A substituted or unsubstituted boron group; And or -SnR _a R _b R _c,
R _a , R _b And R &lt; _c &gt; are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
E2 is a second conjugated monomer different from the first conjugated monomer. The method of claim 11,
The method for preparing the copolymer comprises: adding a first compound to a solvent; A second compound; And dissolving the third compound. A first electrode;
A second electrode facing the first electrode; And
And at least one organic layer disposed between the first electrode and the second electrode and including a photoactive layer,
Wherein at least one of the organic material layers comprises the copolymer according to any one of claims 1 to 9. 14. The method of claim 13,
Wherein the organic material layer includes a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes,
Wherein the hole transport layer, the hole injection layer, or the layer simultaneously transporting the holes and the hole injection comprises the copolymer. 14. The method of claim 13,
Wherein the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport,
Wherein the electron injecting layer, the electron transporting layer, or the layer simultaneously injecting electrons and transporting electrons comprises the copolymer. 14. The method of claim 13,
Wherein the photoactive layer comprises an electron donor and an electron acceptor,
Wherein the electron donor comprises the copolymer. 14. The method of claim 13,
Wherein the organic solar cell further comprises one or more organic layers selected from the group consisting of a hole injecting layer, a hole transporting layer, a hole blocking layer, a charge generating layer, an electron blocking layer, an electron injecting layer and an electron transporting layer. .

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